Protected particles of anode active materials for lithium batteries

1. An anode active material layer for a lithium battery, said anode active material layer comprising multiple particulates of an anode active material, wherein a particulate is composed of one or a plurality of particles of an anode active material being encapsulated by a thin layer of sulfonated elastomeric material that has a fully recoverable tensile strain from 2% to 1000%, a lithium ion conductivity from 10 −7 S/cm to 5×10 −2 S/cm at room temperature, and an encapsulating shell thickness from 1 nm to 10 μm, wherein said sulfonated elastomeric material contains a material selected from sulfonated natural polyisoprene, sulfonated synthetic polyisoprene, sulfonated polybutadiene, sulfonated chloroprene rubber, sulfonated polychloroprene, sulfonated butyl rubber, sulfonated styrene-butadiene rubber, sulfonated nitrile rubber, sulfonated ethylene propylene rubber, sulfonated ethylene propylene diene rubber, sulfonated nietallocene-based poly(ethylene-co-octene) (POE) elastomer, suifoltated polv(etitviene-co-butene) (PBE) elastomer, sulfoltated styrene-ethylene-butadiene-styrene (SEGS) elastomer, sulfonated epichlorohydrin rubber, sulfonated polyacrylic rubber, sulfonated silicone rubber, sulfonated fluorosilicone rubber, sulfonated perfluoroelastomers, sulfonated polyether block amides, sulfonated chlorosulfonated polyethylene, sulfonated ethylene-vinyl acetate polymer, sulfonated protein resilin, sulfonated protein elastin, sulfonated ethylene oxide-epichlorohydrin copolymer, sulfonated polyurethane, sulfonated urethane-urea copolymer, or a combination thereof.

2. The anode active material layer of claim 1 , wherein said anode active material is selected from the group consisting of: (a) silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), titanium (Ti), nickel (Ni), cobalt (Co), and cadmium (Cd); (b) alloys or intermetallic compounds of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Ni, Co, or Cd with other elements; (c) oxides, carbides, nitrides, sulfides, phosphides, selenides, and tellurides of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Ti, Fe, Ni, Co, V, or Cd, and their mixtures, composites, or lithium-containing composites; (d) salts and hydroxides of Sn; (e) lithium titanate, lithium manganate, lithium aluminate, lithium-containing titanium oxide, lithium transition metal oxide; (f) prelithiated versions thereof; (g) particles of Li, Li alloy, or surface-stabilized Li having at least 60% by weight of lithium element therein; and (h) combinations thereof.

3. The anode active material layer of claim 2 , wherein said Li alloy contains from 0.1% to 10% by weight of a metal element selected from Zn, Ag, Au, Mg, Ni, Ti, Fe, Co, V, or a combination.

4. The anode active material layer of claim 1 , wherein said anode active material contains a prelithiated Si, prelithiated Ge, prelithiated Sn, prelithiated SnO x , prelithiated SiO x , prelithiated iron oxide, prelithiated VO 2 , prelithiated Co 3 O 4 , prelithiated Ni 3 O 4 , or a combination thereof, wherein x=1 to 2.

5. The anode active material layer of claim 1 , wherein said anode active material is in a form of nano particle, nano wire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn having a thickness or diameter from 0.5 nm to 100 nm.

6. The anode active material layer of claim 5 , wherein said anode active material has a dimension less than 20 nm.

7. The anode active material layer of claim 1 , wherein said one or a plurality of particles is coated with a layer of carbon disposed between said one or said plurality of particles and said sulfonated elastomeric material layer.

8. The anode active material layer of claim 1 , wherein said particulate further contains a graphite or carbon material therein.

9. The anode active material layer of claim 8 , wherein said graphite or carbon material is selected from polymeric carbon, amorphous carbon, chemical vapor deposition carbon, coal tar pitch, petroleum pitch, mesophase pitch, carbon black, coke, acetylene black, activated carbon, fine expanded graphite particle with a dimension smaller than 100 nm, artificial graphite particle, natural graphite particle, or a combination thereof.

10. The anode active material layer of claim 5 , wherein said nanoparticle, nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn is coated with or embraced by a conductive protective coating selected from a carbon material, electronically conductive polymer, conductive metal oxide, or conductive metal coating.

11. The anode active material layer of claim 10 , wherein said nanoparticle, nanowire, nanofiber, nanotube, nanosheet, nanobelt, nanoribbon, nanodisc, nanoplatelet, or nanohorn is pre-intercalated or pre-doped with lithium ions to form a prelithiated anode active material having an amount of lithium from 0.1% to 54.7%% by weight of said prelithiated anode active material.

12. The anode active material layer of claim 1 , wherein said sulfonated elastomeric material is a rubber or elastomer having no additive or filler dispersed therein.

13. The anode active material layer of claim 1 , wherein said sulfonated elastomeric material is an elastomer matrix composite containing from 0.1% to 50% by weight of a lithium ion-conducting additive dispersed in a sulfonated elastomer matrix material.

14. The anode active material layer of claim 1 , wherein said sulfonated elastomeric material is an elastomer matrix composite containing a lithium ion-conducting additive dispersed in a sulfonated elastomer matrix material, wherein said lithium ion-conducting additive is selected from Li 2 CO 3 , Li 2 O, Li 2 C 2 O 4 , LiOH, LiX, ROCO 2 Li, HCOLi, ROLi, (ROCO 2 Li) 2 , (CH 2 OCO 2 Li) 2 , Li 2 S, Li X SO y , or a combination thereof, wherein X =F, Cl, I, or Br, R =a hydrocarbon group, 0 <x<1, 1<y<4.

15. The anode active material layer of claim 1 , wherein said sulfonated elastomeric material is an elastomer matrix composite containing a lithium ion-conducting additive dispersed in a sulfonated elastomer matrix material, wherein said lithium ion-conducting additive contains a lithium salt selected lithium perchlorate (LiClO4), lithium hexafluorophosphate (LiPF6), lithium borofluoride, (LiBF4), lithium hexafluoroarsenide (LiAsF6), lithium trifluoro-metasulfonate (LiCF3SO3), bis-trifluoromethyl sulfonylimide lithium (LiN(CF3SO2)2), lithium bis(oxalato)borate (LiBOB), lithium oxalyldifluoroborate (LiBF2C2O4), lithium oxalyldifluoroborate (LiBF2C2O4), lithium nitrate (LiNO3) Li-Fluoroalkyl-Phosphates (LiPF3(CF2CF3)3), lithium bisperfluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulphonyl)imide, lithium bis(fluorosulphonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid-based lithium salt, or a combination thereof.

16. The anode active material layer of claim 1 , wherein said sulfonated elastomeric material contains a mixture or blend of a sulfonated elastomer and an electron-conducting polymer selected from polyaniline, polypyrrole, polythiophene, polyfuran, a bi-cyclic polymer, a sulfonated derivative thereof, or a combination thereof.

17. The anode active material layer of claim 1 , wherein said sulfonated elastomeric material contains a mixture or blend of a sulfonated elastomer and a lithium ion-conducting polymer selected from poly(ethylene oxide) (PEO), polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVDF), poly bis-methoxy ethoxyethoxide-phosphazenex, polyvinyl chloride, polydimethylsiloxane, poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), a sulfonated derivative thereof, or a combination thereof.

18. A powder mass of an anode active material for a lithium battery, said powder mass comprising multiple particulates wherein at least a particulate is composed of one or a plurality of particles of an anode active material being encapsulated by a thin layer of sulfonated elastomeric material that has a fully recoverable tensile strain from 5% to 800%, a lithium ion conductivity from 10 −7 S/cm to 5×10 −2 S/cm at room temperature, and an encapsulating shell thickness from 1 nm to 10 μm, and wherein said anode active material has a specific capacity of lithium storage greater than 372 mAh/g, wherein said sulfonated elastomeric material contains a material selected from sulfonated natural polyisoprene, sulfonated synthetic polyisoprene, sulfonated polybutadiene, sulfonated chloroprene rubber, sulfonated polychloroprene, sulfonated butyl rubber, sulfonated styrene-butadiene rubber, sulfonated nitrile rubber, sulfonated ethylene propylene rubber, sulfonated ethylene propylene diene rubber, sulfonated metallocene-based poly(ethylene-co-octene) (POE) elastomer, sulfonated p((ethylene-co-butene) (PBE) elastomer, sulfonated styrene-ethylene-butadiene-styrene (SEBS) elastomer, sulfonated epichlorohydrin rubber, sulfonated polyacrylic rubber, sulfonated silicone rubber, sulfonated fluorosilicone rubber, sulfonated perfluoroelastomers, sulfonated polyether block amides, sulfonated chlorosulfonated polyethylene, sulfonated ethylene-vinyl acetate polymer, sulfonated protein resilin, sulfonated protein elastin, sulfonated ethylene oxide-epichlorohydrin copolymer, sulfonated polyurethane, sulfonated urethane-urea copolymer, or a combination thereof.

19. The powder mass of claim 18 , further comprising graphite particles, carbon particles, mesophase microbeads, carbon or graphite fibers, carbon nanotubes, graphene sheets, or a combination thereof that are mixed with said multiple particulates.

20. The powder mass of claim 18 , wherein said anode active material is pre-lithiated, and contains from 0.1% to 54.7% by weight of lithium.

21. A lithium battery containing an optional anode current collector, the anode active material layer as defined in claim 1 , a cathode active material layer, an optional cathode current collector, an electrolyte in ionic contact with said anode active material layer and said cathode active material layer, and an optional porous separator.

22. The lithium battery of claim 21 , which is a lithium-ion battery, lithium metal battery, lithium-sulfur battery, lithium-selenium battery, or lithium-air battery.